Abstract

The lithium–air (Li–O 2) battery has been deemed one of the most promising next–generation energy–storage devices due to its ultrahigh energy density. However, in conventional porous carbon–air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile–based air cathode is developed with a triple–phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile–based Li–O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm –2, a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile–based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. In conclusion, the reported decoupled transport pathway design also spurs potential toward flexible/wearable Li–O 2 batteries.

The rapid development of wearable electronics requires a revolution of power accessories regarding flexibility and energy density. The Li–CO 2 battery was recently proposed as a novel and promising candidate for next-generation energy-storage systems. However, the current Li–CO 2 batteries usually suffer from the difficulties of poor stability, low energy efficiency, and leakage of liquid electrolyte, and few flexible Li–CO 2 batteries for wearable electronics have been reported so far. Herein, a quasi-solid-state flexible fiber-shaped Li–CO 2 battery with low overpotential and high energy efficiency, by employing ultrafine Mo 2C nanoparticles anchored on a carbon nanotube (CNT) cloth freestanding hybridmore » film as the cathode, is demonstrated. Due to the synergistic effects of the CNT substrate and Mo 2C catalyst, it achieves a low charge potential below 3.4 V, a high energy efficiency of approximate to 80%, and can be reversibly discharged and charged for 40 cycles. Experimental results and theoretical simulation show that the intermediate discharge product Li 2C 2O 4 stabilized by Mo 2C via coordinative electrons transfer should be responsible for the reduction of overpotential. Here, the as-fabricated quasi-solid-state flexible fiber-shaped Li–CO 2 battery can also keep working normally even under various deformation conditions, giving it great potential of becoming an advanced energy accessory for wearable electronics.« less

Lithium-oxygen (Li-O 2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B 4C) as the non-carbon based oxygen electrode material for aprotic Li-O 2 batteries. B 4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable formore » battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O 2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B 4C based electrode is mainly due to be the loss of active sites on B 4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B 4C is a very promising alternative oxygen electrode material for aprotic Li-O 2 batteries. It can also be used as a standard electrode to investigate the stability of electrolytes.« less

The transport of oxygen in a porous perovskite solid oxide fuel cell cathode is modeled by use of the principles of porous electrode modeling, by taking into account exchange kinetics at the gas/electrode interface, bulk diffusion of oxygen vacancies, surface diffusion of adsorbed oxygen atoms, and electrochemical kinetics at the cathode/electrolyte interface. The mechanism for the latter is based on the assumption that intermediately adsorbed oxygen atoms are reduced at the cathode/electrolyte interface in favor of direct exchange of oxygen vacancies. The significance of concentration polarization is demonstrated even at very low overpotentials, especially if the adsorption process is slow.more » Under such conditions, the empirical correlation R{sub p}{sup eff} {proportional_to} p{sub O{sub 2}}{sup {minus}m} claimed to exist between the measured potential resistance and the partial pressure of oxygen cannot be justified on fundamental grounds. A limiting current is obtained at high cathodic overpotentials due to the depletion of intermediately adsorbed species at the cathode/electrolyte interface. The existence of a correlation i{sub lim} {proportional_to} p{sub O{sub 2}}{sup n} is predicted, where the exponent n is determined by the kinetic and transport properties of the cathode for oxygen exchange and transport.« less

The temperature dependence of the oxygen reduction mechanism in Li-O 2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O 2 batteries decreases from 7,492 mAh g -1 at 40C to 2,930 mAh g -1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g -1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C tomore » 40C, the morphologies of the Li 2O 2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O 2 battery and will enable a more rational design of Li-O 2 batteries.« less